EP0483923A1 - Hydrodenitrification process - Google Patents
Hydrodenitrification process Download PDFInfo
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- EP0483923A1 EP0483923A1 EP91202785A EP91202785A EP0483923A1 EP 0483923 A1 EP0483923 A1 EP 0483923A1 EP 91202785 A EP91202785 A EP 91202785A EP 91202785 A EP91202785 A EP 91202785A EP 0483923 A1 EP0483923 A1 EP 0483923A1
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- Prior art keywords
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 102
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 5
- -1 nitrogen-containing hydrocarbons Chemical class 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012043 cost effectiveness analysis Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
Definitions
- This invention relates to a hydrotreating process for the removal of nitrogen-containing compounds from petroleum fractions.
- Nitrogen-containing compounds in petroleum fractions can adversely affect end products.
- nitrogen compounds can adversely affect the storage stability and octane value of naphthas and may poison downstream catalysts.
- Nitrogen removal improves air quality to some extent, since it lowers the potential for NO x formation during subsequent fuel combustion. Crude and other heavy petroleum fractions are typically subjected to hydrodenitrification prior to being subjected to further processing.
- a "stacked" or multiple bed hydrotreating system has now been developed for removal of nitrogen-containing feedstocks comprising a Ni-W-optionally P/alumina catalyst "stacked" on top of a Ni-Mo-optionally P/alumina catalyst which offers activity advantages over the individual catalysts for hydrodenitrification.
- a more active catalyst can be operated at a lower temperature to obtain the same degree of nitrogen conversion as a less active catalyst.
- a lower operating temperature will prolong catalyst life and decrease operating expenses.
- the present invention comprises a process for the hydrogenation of nitrogen-containing hydrocarbons in a hydrocarbon feedstock having a nitrogen content greater than 150 ppm which process comprises:
- the present process can be operated at lower temperatures than processes using individual hydrodenitrification catalysts.
- the present invention relates to a process for reducing the nitrogen content of a hydrocarbon feedstock by contacting the feedstock in the presence of added hydrogen with a two bed catalyst system at hydrotreating and mild hydrocracking conditions, i.e., at conditions of temperature and pressure and amounts of added hydrogen such that significant quantities of nitrogen-containing hydrocarbons are reacted with hydrogen to produce gaseous nitrogen compounds which are removed from the feedstock.
- the feedstock to be utilized is any crude or petroleum fraction containing in excess of 150 parts per million by weight (ppm) of nitrogen in the form of nitrogen-containing hydrocarbons, suitably more than 300 ppm, preferably more than 500 ppm, most preferably more than 750 ppm.
- suitable petroleum fractions include catalytically cracked light and heavy gas oils, straight run heavy gas oils, light flash distillates, light cycle oils, vacuum gas oils, coker gas oil, synthetic gas oil and mixtures thereof.
- the feedstocks that are most advantageously processed by the instant invention are feedstocks for first stage hydrocracking units. These feedstocks will usually also contain from 0.01 to 2, preferably from 0.05 to 1.5 percent by weight of sulfur present as organosulfur compounds.
- Feedstocks with very high sulfur contents are generally not suitable for processing in the instant process.
- Feedstocks with very high sulfur contents can be subjected to a separate hydrodesulfurization process in order to reduce their sulfur contents to 0.01-2, preferably 0.05-1.5 percent by weight prior to being processed by the present process.
- the present process utilizes two catalyst beds in series.
- the first catalyst bed is made up of a hydrotreating catalyst comprising nickel, tungsten and optionally phosphorous supported on an alumina support and the second catalyst bed is made up of a hydrotreating catalyst comprising nickel, molybdenum and optionally phosphorous supported on an alumina support.
- first refers to the first bed with which the feedstock is contacted and "second” refers to the bed with which the feedstock, after passing through the first bed, is next contacted.
- the two catalyst beds may be distributed through two or more reactors, or, in the preferred embodiment, they are contained in one reactor.
- the reactor(s) used in the instant process is used in the trickle phase mode of operation, that is, feedstock and hydrogen are fed to the top of the reactor and the feedstock trickles down through the catalyst bed primarily under the influence of gravity.
- the feedstock with added hydrogen is fed to the first catalyst bed and the feedstock as it exits from the first catalyst bed is passed directly to the second catalyst bed without modification.
- “Without modification” means that no (substantial) sidestreams of hydrocarbon materials are removed from or added to the stream passing between the two catalyst beds.
- Hydrogen may be added at more than one position in the reactor(s) in order to maintain control of the temperature.
- the first bed is also referred to as the "top" bed.
- the volume ratio of the first catalyst bed to the second catalyst bed is primarily determined by a cost effectiveness analysis and the nitrogen and sulfur contents of the feed to be processed.
- the cost of the first bed catalyst which contains more expensive tungsten is approximately two to three times the cost of the second bed catalyst which contains less expensive molybdenum.
- the optimum volume ratio will depend on the particular feedstock nitrogen and sulfur contents and will be optimized to provide minimum overall catalyst cost and maximum nitrogen removal.
- the volume ratio of the first catalyst bed to the second catalyst bed will range from 1:5 to 5:1, more preferably from 1:4 to 4:1, and most preferably from 1:3 to 3:1.
- the volume of the first catalyst will be equal to or less than the volume of the second catalyst, that is the volume of the first catalyst will comprise from 10 percent to 50 percent of the total bed volume.
- the catalyst utilized in the first bed comprises nickel, tungsten and 0-5% wt phosphorous (measured as the element) supported on a porous alumina support preferably comprising gamma alumina. It contains from 1 to 5, preferably from 2 to 4 percent by weight of nickel (measured as the metal); from 15 to 35, preferably from 20 to 30 percent by weight of tungsten (measured as the metal) and, when present, preferably from 1 to 5, more preferably from 2 to 4 percent by weight of phosphorous (measured as the element), all per total weight of the catalyst. It will have a surface area, as measured by the B.E.T. method (Brunauer et al, J. Am. Chem. Soc., 60 , 309-16 (1938)) of greater than 100 m2/g and a water pore volume between 0.2 to 0.6, preferably between 0.3 to 0.5.
- the catalyst utilized in the second bed comprises nickel, molybdenum and 0-5% wt phosphorous (measured as the element) supported on a porous alumina support preferably comprising gamma alumina. It contains from 1 to 5, preferably from 2 to 4 percent by weight of nickel (measured as the metal); from 8 to 20, preferably from 12 to 16 percent by weight of molybdenum (measured as the metal) and, when present, preferably from 1 to 5, more preferably from 2 to 4 percent by weight of phosphorous (measured as the element), all per total weight of the catalyst. It will have a surface area, as measured by the B.E.T. method, of greater than 120 m2/g and a water pore volume between 0.2 to 0.6, preferably between 0.3 to 0.5.
- the catalyst utilized in both beds of the present process are catalysts that are known in the hydrocarbon hydroprocessing art. These catalysts are made in a conventional fashion as described in the prior art. For example porous alumina pellets can be impregnated with solution(s) containing nickel, tungsten or molybdenum and phosphorous compounds, the pellets subsequently dried and calcined at elevated temperatures. Alternately, one or more of the components can be incorporated into an alumina powder by mulling, the mulled powder formed into pellets and calcined at elevated temperature. Combinations of impregnation and mulling can be utilized. Other suitable methods can be found in the prior art. Non-limiting examples of catalyst preparative techniques can be found in U.S.
- the catalysts are typically formed into various sizes and shapes. They may be suitably shaped into particles, chunks, pieces, pellets, rings, spheres, wagon wheels, and polylobes, such as bilobes, trilobes and tetralobes.
- the two above-described catalysts are normally presulfided prior to use.
- the catalysts are presulfided by heating in H2S/H2 atmosphere at elevated temperatures.
- a suitable presulfiding regimen comprises heating the catalysts in a hydrogen sulfide/hydrogen atmosphere (5%v H2S/95%v H2) for about two hours at about 371 °C.
- Other methods are also suitable for presulfiding and generally comprise heating the catalysts to elevated temperatures (e.g., 204-399 °C) in the presence of hydrogen and a sulfur-containing material.
- the hydrogenation process of the present invention is effected at a temperature between 302 °C and 413 °C, preferably between 316 °C and 413 °C under pressures above 39 bar.
- the total pressure will typically range from 40 bar to 168 bar.
- the hydrogen partial pressure will typically range from 35 bar to 149 bar.
- the hydrogen feed rate will typically range from 178 to 1069 vol/vol.
- the feedstock rate will typically have a liquid hourly space velocity ("LHSV") ranging from 0.1 to 5, preferably from 0.2 to 3.
- LHSV liquid hourly space velocity
- catalysts were tested utilizing the catalysts noted in Table 1: A/B, B/A, A and B.
- the catalysts were diluted with 60/80 mesh silicon carbide particles in a 1:1 volume ratio of catalyst:carbide and 100 cc of the mixture was used in the catalyst bed.
- the catalysts were presulfided in the reactor by heating them to about 371 °C and holding at such temperature for about two hours in a 95 vol.% hydrogen-5 vol.% hydrogen sulfide atmosphere flowing at a rate of about 120 liters/hour.
- the feeds from table 2 were passed down through the catalyst bed at a liquid hourly space velocity of 1 hour ⁇ 1, a system pressure of 119 bar and a hydrogen flow rate of about 100 liters/hr.
- the reactor temperature was adjusted to provide a liquid product containing 5 ppm of nitrogen as measured by chemiluminescence.
- the catalysts were run for about 600 hours. From the temperature required to obtain 5 ppm nitrogen in the product versus time, it was noted that the catalysts had stabilized at about 200 hours. A best fit line was drawn through the stabilized portions of the curves and the temperatures required for 5 ppm of nitrogen were obtained after a run time of 300 hours and are given in Table 3 below.
- the present invention provides for enhanced catalyst activity (lower temperature to achieve 5 ppm N) when compared to the individual catalysts and when compared to a stacked bed of catalyst B over catalyst A.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
Description
- This invention relates to a hydrotreating process for the removal of nitrogen-containing compounds from petroleum fractions.
- Nitrogen-containing compounds in petroleum fractions can adversely affect end products. For example, nitrogen compounds can adversely affect the storage stability and octane value of naphthas and may poison downstream catalysts. Nitrogen removal improves air quality to some extent, since it lowers the potential for NOx formation during subsequent fuel combustion. Crude and other heavy petroleum fractions are typically subjected to hydrodenitrification prior to being subjected to further processing.
- A "stacked" or multiple bed hydrotreating system has now been developed for removal of nitrogen-containing feedstocks comprising a Ni-W-optionally P/alumina catalyst "stacked" on top of a Ni-Mo-optionally P/alumina catalyst which offers activity advantages over the individual catalysts for hydrodenitrification. A more active catalyst can be operated at a lower temperature to obtain the same degree of nitrogen conversion as a less active catalyst. A lower operating temperature will prolong catalyst life and decrease operating expenses.
- The prior art discloses several examples of stacked catalyst beds used to hydroprocess petroleum fractions, such as US patent specifications 3,392,112; 3,766,058; 3,876,530; 4,016,067; 4,016,069; 4,016,070; 4,012,330; 4,048,060; 4,166,026; 4,392,945; 4,406,779; 4,421,633; 4,431,526; 4,447,314; 4,534,852 and 4,776,945.
- Further, in European application No. 91201649.0, there is described the use of a stacked bed of Ni-W-optionally P/alumina catalyst on top of a Co and/or Ni-Mo-optionally P/alumina catalyst for use in a hydrotreating process to saturate aromatics in diesel boiling-range hydrocarbon feedstocks.
- The present invention comprises a process for the hydrogenation of nitrogen-containing hydrocarbons in a hydrocarbon feedstock having a nitrogen content greater than 150 ppm which process comprises:
- (a) contacting at a temperature between 302 °C and 413 °C and a pressure between 40 bar and 168 bar in the presence of added hydrogen the feedstock with a first catalyst bed containing a hydrotreating catalyst comprising nickel and tungsten supported on an alumina support, and
- (b) passing the hydrogen and feedstock without modification, from the first catalyst bed to a second catalyst bed where it is contacted at a temperature between 302 °C and 413 °C and a pressure between 40 bar and 168 bar with a hydrotreating catalyst comprising nickel and molybdenum supported on an alumina support.
- The present process can be operated at lower temperatures than processes using individual hydrodenitrification catalysts.
- The present invention relates to a process for reducing the nitrogen content of a hydrocarbon feedstock by contacting the feedstock in the presence of added hydrogen with a two bed catalyst system at hydrotreating and mild hydrocracking conditions, i.e., at conditions of temperature and pressure and amounts of added hydrogen such that significant quantities of nitrogen-containing hydrocarbons are reacted with hydrogen to produce gaseous nitrogen compounds which are removed from the feedstock.
- The feedstock to be utilized is any crude or petroleum fraction containing in excess of 150 parts per million by weight (ppm) of nitrogen in the form of nitrogen-containing hydrocarbons, suitably more than 300 ppm, preferably more than 500 ppm, most preferably more than 750 ppm. Examples of suitable petroleum fractions include catalytically cracked light and heavy gas oils, straight run heavy gas oils, light flash distillates, light cycle oils, vacuum gas oils, coker gas oil, synthetic gas oil and mixtures thereof. Typically, the feedstocks that are most advantageously processed by the instant invention are feedstocks for first stage hydrocracking units. These feedstocks will usually also contain from 0.01 to 2, preferably from 0.05 to 1.5 percent by weight of sulfur present as organosulfur compounds. Feedstocks with very high sulfur contents are generally not suitable for processing in the instant process. Feedstocks with very high sulfur contents can be subjected to a separate hydrodesulfurization process in order to reduce their sulfur contents to 0.01-2, preferably 0.05-1.5 percent by weight prior to being processed by the present process.
- The present process utilizes two catalyst beds in series. The first catalyst bed is made up of a hydrotreating catalyst comprising nickel, tungsten and optionally phosphorous supported on an alumina support and the second catalyst bed is made up of a hydrotreating catalyst comprising nickel, molybdenum and optionally phosphorous supported on an alumina support. The term "first" as used herein refers to the first bed with which the feedstock is contacted and "second" refers to the bed with which the feedstock, after passing through the first bed, is next contacted. The two catalyst beds may be distributed through two or more reactors, or, in the preferred embodiment, they are contained in one reactor. In general the reactor(s) used in the instant process is used in the trickle phase mode of operation, that is, feedstock and hydrogen are fed to the top of the reactor and the feedstock trickles down through the catalyst bed primarily under the influence of gravity. Whether one or more reactors are utilized, the feedstock with added hydrogen is fed to the first catalyst bed and the feedstock as it exits from the first catalyst bed is passed directly to the second catalyst bed without modification. "Without modification" means that no (substantial) sidestreams of hydrocarbon materials are removed from or added to the stream passing between the two catalyst beds. Hydrogen may be added at more than one position in the reactor(s) in order to maintain control of the temperature. When both beds are contained in one reactor, the first bed is also referred to as the "top" bed.
- The volume ratio of the first catalyst bed to the second catalyst bed is primarily determined by a cost effectiveness analysis and the nitrogen and sulfur contents of the feed to be processed. The cost of the first bed catalyst which contains more expensive tungsten is approximately two to three times the cost of the second bed catalyst which contains less expensive molybdenum. The optimum volume ratio will depend on the particular feedstock nitrogen and sulfur contents and will be optimized to provide minimum overall catalyst cost and maximum nitrogen removal. In general terms the volume ratio of the first catalyst bed to the second catalyst bed will range from 1:5 to 5:1, more preferably from 1:4 to 4:1, and most preferably from 1:3 to 3:1. In a particularly preferred embodiment the volume of the first catalyst will be equal to or less than the volume of the second catalyst, that is the volume of the first catalyst will comprise from 10 percent to 50 percent of the total bed volume.
- The catalyst utilized in the first bed comprises nickel, tungsten and 0-5% wt phosphorous (measured as the element) supported on a porous alumina support preferably comprising gamma alumina. It contains from 1 to 5, preferably from 2 to 4 percent by weight of nickel (measured as the metal); from 15 to 35, preferably from 20 to 30 percent by weight of tungsten (measured as the metal) and, when present, preferably from 1 to 5, more preferably from 2 to 4 percent by weight of phosphorous (measured as the element), all per total weight of the catalyst. It will have a surface area, as measured by the B.E.T. method (Brunauer et al, J. Am. Chem. Soc., 60, 309-16 (1938)) of greater than 100 m²/g and a water pore volume between 0.2 to 0.6, preferably between 0.3 to 0.5.
- The catalyst utilized in the second bed comprises nickel, molybdenum and 0-5% wt phosphorous (measured as the element) supported on a porous alumina support preferably comprising gamma alumina. It contains from 1 to 5, preferably from 2 to 4 percent by weight of nickel (measured as the metal); from 8 to 20, preferably from 12 to 16 percent by weight of molybdenum (measured as the metal) and, when present, preferably from 1 to 5, more preferably from 2 to 4 percent by weight of phosphorous (measured as the element), all per total weight of the catalyst. It will have a surface area, as measured by the B.E.T. method, of greater than 120 m²/g and a water pore volume between 0.2 to 0.6, preferably between 0.3 to 0.5.
- The catalyst utilized in both beds of the present process are catalysts that are known in the hydrocarbon hydroprocessing art. These catalysts are made in a conventional fashion as described in the prior art. For example porous alumina pellets can be impregnated with solution(s) containing nickel, tungsten or molybdenum and phosphorous compounds, the pellets subsequently dried and calcined at elevated temperatures. Alternately, one or more of the components can be incorporated into an alumina powder by mulling, the mulled powder formed into pellets and calcined at elevated temperature. Combinations of impregnation and mulling can be utilized. Other suitable methods can be found in the prior art. Non-limiting examples of catalyst preparative techniques can be found in U.S. patent specifications 4,530,911, and 4,520,128. The catalysts are typically formed into various sizes and shapes. They may be suitably shaped into particles, chunks, pieces, pellets, rings, spheres, wagon wheels, and polylobes, such as bilobes, trilobes and tetralobes.
- The two above-described catalysts are normally presulfided prior to use. Typically, the catalysts are presulfided by heating in H₂S/H₂ atmosphere at elevated temperatures. For example, a suitable presulfiding regimen comprises heating the catalysts in a hydrogen sulfide/hydrogen atmosphere (5%v H₂S/95%v H₂) for about two hours at about 371 °C. Other methods are also suitable for presulfiding and generally comprise heating the catalysts to elevated temperatures (e.g., 204-399 °C) in the presence of hydrogen and a sulfur-containing material.
- The hydrogenation process of the present invention is effected at a temperature between 302 °C and 413 °C, preferably between 316 °C and 413 °C under pressures above 39 bar. The total pressure will typically range from 40 bar to 168 bar. The hydrogen partial pressure will typically range from 35 bar to 149 bar. The hydrogen feed rate will typically range from 178 to 1069 vol/vol. The feedstock rate will typically have a liquid hourly space velocity ("LHSV") ranging from 0.1 to 5, preferably from 0.2 to 3.
- The invention will be further described by the following examples which are provided for illustrative purposes and are not to be construed as limiting the invention.
-
-
- Four types of catalyst configurations were tested utilizing the catalysts noted in Table 1: A/B, B/A, A and B. The catalysts were diluted with 60/80 mesh silicon carbide particles in a 1:1 volume ratio of catalyst:carbide and 100 cc of the mixture was used in the catalyst bed. The catalysts were presulfided in the reactor by heating them to about 371 °C and holding at such temperature for about two hours in a 95 vol.% hydrogen-5 vol.% hydrogen sulfide atmosphere flowing at a rate of about 120 liters/hour.
- To test the catalysts, the feeds from table 2 were passed down through the catalyst bed at a liquid hourly space velocity of 1 hour⁻¹, a system pressure of 119 bar and a hydrogen flow rate of about 100 liters/hr. The reactor temperature was adjusted to provide a liquid product containing 5 ppm of nitrogen as measured by chemiluminescence. The catalysts were run for about 600 hours. From the temperature required to obtain 5 ppm nitrogen in the product versus time, it was noted that the catalysts had stabilized at about 200 hours. A best fit line was drawn through the stabilized portions of the curves and the temperatures required for 5 ppm of nitrogen were obtained after a run time of 300 hours and are given in Table 3 below.
Table 3 Comparative Hydrodenitrification Results Bed Loading A vol./B vol. Temp. Required for 5 ppm Nitrogen, °C FEED A FEED B 20/80 349 340 30/70 349 336 100/0 354 - 0/100 352 344 80/20 353 - 60/40 356 - - As can be seen from the above data, the present invention provides for enhanced catalyst activity (lower temperature to achieve 5 ppm N) when compared to the individual catalysts and when compared to a stacked bed of catalyst B over catalyst A.
Claims (8)
- A process for the hydrogenation of nitrogen-containing hydrocarbons in a hydrocarbon feedstock having a nitrogen content greater than 150 parts per million by weight which process comprises:(a) contacting at a temperature between 302 °C and 413 °C and a pressure between 40 bar and 168 bar in the presence of added hydrogen the feedstock with a first catalyst bed containing a hydrotreating catalyst comprising nickel and tungsten supported on an alumina support, and(b) passing the hydrogen and feedstock without modification, from the first catalyst bed to a second catalyst bed where it is contacted at a temperature between 302 °C and 413 °C and a pressure between 40 bar and 168 bar with a hydrotreating catalyst comprising nickel and molybdenum supported on an alumina support.
- The process of claim 1 wherein the support for the catalyst in the first catalyst bed has a surface area greater than 100 m²/g and a water pore volume ranging from 0.2 to 0.6 cc/g and the support for the catalyst in the second catalyst bed has a surface area greater than 120 m²/g and a water pore volume ranging from 0.2 to 0.6 cc/g.
- The process of claim 1 or 2 wherein the supports for both catalysts have water pore volumes ranging between from 0.3 to 0.5 cc/g.
- The process of any one of claims 1-3 wherein in the catalyst in the first bed the nickel content ranges from 1 to 5 percent by weight of the total catalyst, measured as the metal and the tungsten content ranges from 15 to 35 percent by weight of the total catalyst, measured as the metal and wherein in the catalyst in the second bed the nickel content ranges from 1 to 5 percent by weight of the total catalyst, measured as the metal and the molybdenum content ranges from 8 to 20 percent by weight of the total catalyst, measured as the metal.
- The process of any one of claims 1-4 wherein in the catalyst in the first bed the nickel content ranges from 2 to 4 percent by weight of the total catalyst, measured as the metal and the tungsten content ranges from 20 to 30 percent by weight of the total catalyst, measured as the metal and wherein in the catalyst in the second bed the nickel content ranges from 2 to 4 percent by weight of the total catalyst, measured as the metal and the molybdenum content ranges from 12 to 16 percent by weight of the total catalyst, measured as the metal.
- The process of any one of claims 1-5 wherein the catalyst in the first catalyst bed and/or the catalyst in the second catalyst bed additionally comprise phosphorus.
- The process of any one of claims 1-6 wherein in the catalyst in the first bed the phosphorous content ranges from 2 to 4 percent by weight of the total catalyst, measured as the element and wherein in the catalyst in the second bed the phosphorous content ranges from 2 to 4 percent by weight of the total catalyst, measured as the element.
- The process of any one of claims 1-7 wherein the temperature in steps (a) and (b) ranges from 316 °C to 413 °C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60641490A | 1990-10-31 | 1990-10-31 | |
US606414 | 1990-10-31 |
Publications (2)
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EP0483923A1 true EP0483923A1 (en) | 1992-05-06 |
EP0483923B1 EP0483923B1 (en) | 1996-02-28 |
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EP91202785A Expired - Lifetime EP0483923B1 (en) | 1990-10-31 | 1991-10-28 | Hydrodenitrification process |
Country Status (11)
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US (1) | US5116484A (en) |
EP (1) | EP0483923B1 (en) |
JP (1) | JP3054966B2 (en) |
KR (1) | KR0177168B1 (en) |
AT (1) | ATE134696T1 (en) |
AU (1) | AU634428B2 (en) |
CA (1) | CA2054434C (en) |
DE (1) | DE69117433T2 (en) |
DK (1) | DK0483923T3 (en) |
ES (1) | ES2084091T3 (en) |
NZ (1) | NZ240374A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1033399A2 (en) * | 1999-03-03 | 2000-09-06 | Fina Technology, Inc. | Methods for reducing sulfur and carbon in petroleum refining processes |
EP2962753A1 (en) * | 2014-07-04 | 2016-01-06 | IFP Energies nouvelles | Hydrotreating catalyst with high molybdenum density and its method of preparation |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2840620B1 (en) * | 2002-06-07 | 2004-07-30 | Inst Francais Du Petrole | PROCESS FOR PRODUCING LOW SULFUR AND NITROGEN HYDROCARBONS |
US20050113250A1 (en) * | 2003-11-10 | 2005-05-26 | Schleicher Gary P. | Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams |
US20050109679A1 (en) * | 2003-11-10 | 2005-05-26 | Schleicher Gary P. | Process for making lube oil basestocks |
US7816299B2 (en) * | 2003-11-10 | 2010-10-19 | Exxonmobil Research And Engineering Company | Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams |
JP4576257B2 (en) * | 2004-02-10 | 2010-11-04 | Jx日鉱日石エネルギー株式会社 | Production method of oil fraction |
FR3013721B1 (en) * | 2013-11-28 | 2015-11-13 | Ifp Energies Now | GASOLINE HYDROTREATMENT PROCESS USING A CATALYST SURFACE |
KR101623549B1 (en) | 2015-04-17 | 2016-06-07 | 주식회사 세롬 | A tube for packing and its manufacturing method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4406779A (en) * | 1981-11-13 | 1983-09-27 | Standard Oil Company (Indiana) | Multiple catalyst system for hydrodenitrogenation of high nitrogen feeds |
EP0203228A1 (en) * | 1985-05-21 | 1986-12-03 | Shell Internationale Researchmaatschappij B.V. | Single-stage hydrotreating process |
WO1990013363A1 (en) * | 1989-05-10 | 1990-11-15 | Chevron Research And Technology Company | Catalyst system and process for hydrotreating hydrocarbons |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3392112A (en) * | 1965-03-11 | 1968-07-09 | Gulf Research Development Co | Two stage process for sulfur and aromatic removal |
PL72593B1 (en) * | 1968-02-14 | 1974-08-31 | ||
US3798156A (en) * | 1971-09-22 | 1974-03-19 | Standard Oil Co | Hydroprocessing catalyst and process |
US3876530A (en) * | 1973-08-22 | 1975-04-08 | Gulf Research Development Co | Multiple stage hydrodesulfurization with greater sulfur and metal removal in initial stage |
US4012330A (en) * | 1975-02-10 | 1977-03-15 | Exxon Research & Engineering Co. | Lithium salts of hydrocarbon substituted amic acid as low ash rust inhibitors |
US4016070A (en) * | 1975-11-17 | 1977-04-05 | Gulf Research & Development Company | Multiple stage hydrodesulfurization process with extended downstream catalyst life |
US4016069A (en) * | 1975-11-17 | 1977-04-05 | Gulf Research & Development Company | Multiple stage hydrodesulfurization process including partial feed oil by-pass of first stage |
US4048060A (en) * | 1975-12-29 | 1977-09-13 | Exxon Research And Engineering Company | Two-stage hydrodesulfurization of oil utilizing a narrow pore size distribution catalyst |
JPS5850636B2 (en) * | 1977-07-15 | 1983-11-11 | 千代田化工建設株式会社 | Desulfurization treatment method for heavy hydrocarbon oil |
US4421633A (en) * | 1981-03-13 | 1983-12-20 | Mobil Oil Corporation | Low pressure cyclic hydrocracking process using multi-catalyst bed reactor for heavy liquids |
US4392945A (en) * | 1982-02-05 | 1983-07-12 | Exxon Research And Engineering Co. | Two-stage hydrorefining process |
US4447314A (en) * | 1982-05-05 | 1984-05-08 | Mobil Oil Corporation | Demetalation, desulfurization, and decarbonization of petroleum oils by hydrotreatment in a dual bed system prior to cracking |
US4431526A (en) * | 1982-07-06 | 1984-02-14 | Union Oil Company Of California | Multiple-stage hydroprocessing of hydrocarbon oil |
US4540483A (en) * | 1982-08-16 | 1985-09-10 | Union Oil Company Of California | Hydrotreating process |
US4886594A (en) * | 1982-12-06 | 1989-12-12 | Amoco Corporation | Hydrotreating catalyst and process |
JPS59132945A (en) * | 1983-01-21 | 1984-07-31 | Shokubai Kasei Kogyo Kk | Hydro-demetalation catalyst and use thereof |
US4520128A (en) * | 1983-12-19 | 1985-05-28 | Intevep, S.A. | Catalyst having high metal retention capacity and good stability for use in the demetallization of heavy crudes and method of preparation of same |
US4530911A (en) * | 1984-05-18 | 1985-07-23 | Shell Oil Company | Hydrodenitrification catalyst |
US4534852A (en) * | 1984-11-30 | 1985-08-13 | Shell Oil Company | Single-stage hydrotreating process for converting pitch to conversion process feedstock |
US4776945A (en) * | 1984-11-30 | 1988-10-11 | Shell Oil Company | Single-stage hydrotreating process |
US4738767A (en) * | 1985-03-14 | 1988-04-19 | Union Oil Company Of California | Mild hydrocracking with a catalyst containing silica-alumina |
US4619759A (en) * | 1985-04-24 | 1986-10-28 | Phillips Petroleum Company | Two-stage hydrotreating of a mixture of resid and light cycle oil |
US4728417A (en) * | 1986-07-21 | 1988-03-01 | Phillips Petroleum Company | Hydrofining process for hydrocarbon containing feed streams |
-
1991
- 1991-02-11 US US07/653,216 patent/US5116484A/en not_active Expired - Lifetime
- 1991-10-28 ES ES91202785T patent/ES2084091T3/en not_active Expired - Lifetime
- 1991-10-28 DE DE69117433T patent/DE69117433T2/en not_active Expired - Fee Related
- 1991-10-28 EP EP91202785A patent/EP0483923B1/en not_active Expired - Lifetime
- 1991-10-28 DK DK91202785.1T patent/DK0483923T3/en active
- 1991-10-28 KR KR1019910018982A patent/KR0177168B1/en not_active IP Right Cessation
- 1991-10-28 AT AT91202785T patent/ATE134696T1/en not_active IP Right Cessation
- 1991-10-29 CA CA002054434A patent/CA2054434C/en not_active Expired - Fee Related
- 1991-10-29 NZ NZ240374A patent/NZ240374A/en not_active IP Right Cessation
- 1991-10-29 JP JP3308345A patent/JP3054966B2/en not_active Expired - Fee Related
- 1991-10-29 AU AU86845/91A patent/AU634428B2/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4406779A (en) * | 1981-11-13 | 1983-09-27 | Standard Oil Company (Indiana) | Multiple catalyst system for hydrodenitrogenation of high nitrogen feeds |
EP0203228A1 (en) * | 1985-05-21 | 1986-12-03 | Shell Internationale Researchmaatschappij B.V. | Single-stage hydrotreating process |
WO1990013363A1 (en) * | 1989-05-10 | 1990-11-15 | Chevron Research And Technology Company | Catalyst system and process for hydrotreating hydrocarbons |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1033399A2 (en) * | 1999-03-03 | 2000-09-06 | Fina Technology, Inc. | Methods for reducing sulfur and carbon in petroleum refining processes |
EP1033399A3 (en) * | 1999-03-03 | 2001-03-07 | Fina Technology, Inc. | Methods for reducing sulfur and carbon in petroleum refining processes |
EP2962753A1 (en) * | 2014-07-04 | 2016-01-06 | IFP Energies nouvelles | Hydrotreating catalyst with high molybdenum density and its method of preparation |
FR3023184A1 (en) * | 2014-07-04 | 2016-01-08 | IFP Energies Nouvelles | HYDROPROCESSING CATALYST WITH HIGH MOLYBDENES DENSITY AND METHOD OF PREPARATION. |
CN105312069A (en) * | 2014-07-04 | 2016-02-10 | Ifp新能源公司 | Hydrotreatment catalyst with a high density of molybdenum, and process for its preparation |
US10058852B2 (en) | 2014-07-04 | 2018-08-28 | IFP Energies Nouvelles | Hydrotreatment catalyst with a high density of molybdenum, and process for its preparation |
Also Published As
Publication number | Publication date |
---|---|
DK0483923T3 (en) | 1996-04-29 |
ES2084091T3 (en) | 1996-05-01 |
EP0483923B1 (en) | 1996-02-28 |
KR0177168B1 (en) | 1999-04-01 |
US5116484A (en) | 1992-05-26 |
JP3054966B2 (en) | 2000-06-19 |
AU8684591A (en) | 1992-05-07 |
ATE134696T1 (en) | 1996-03-15 |
DE69117433T2 (en) | 1996-08-01 |
KR920008170A (en) | 1992-05-27 |
NZ240374A (en) | 1992-09-25 |
JPH04288397A (en) | 1992-10-13 |
AU634428B2 (en) | 1993-02-18 |
CA2054434C (en) | 2002-12-10 |
CA2054434A1 (en) | 1992-05-01 |
DE69117433D1 (en) | 1996-04-04 |
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